Refrigerant releasing composite

ABSTRACT

A composite configured to release refrigerant therefrom comprises a substrate material comprising polarized fibers of glass, polyamide, phenylene sulfide, carbon or graphite or combinations of two or more thereof having bonded thereon a metal compound comprising a complex compound of a polar gaseous refrigerant and a metal salt and/or a hydrated metal hydroxide and/or a metal hydroxide of a metal comprising alkali metal, alkaline earth metal, transition metal, zinc, cadmium, tin, aluminum, or two or more thereof, at a concentration of at least about 0.3 grams/cc of open substrate material volume, and a coating composition sealing one or more layers of the substrate and/or the exterior composite surface configured to prevent release of internal gaseous refrigerant therethrough at ambient temperatures and pressure and capable of penetration of gaseous refrigerant therethrough from the composite interior at temperatures causing internal gas pressures of 15% or more above exterior pressure for such refrigerant release.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 11/029686 filed Jan. 4, 2005.

BACKGROUND OF THE INVENTION

Materials presently available for protecting vehicles, ammunition,solid, liquid or gaseous fuels, rockets, missiles and/or personnel fromsmall arms projectile penetration or penetration from flying shrapnel,fire, directed energy, explosions and associated heat and the like arerelatively expensive. Moreover, such materials do not have self coolingand/or fire extinguishing properties. The composites described hereinare relatively inexpensive and cost-effective to manufacture, may beproduced in almost any shape, size and thickness, and are recyclable.The composites are configured to release gaseous refrigerant attemperatures above about 150° F. and preferably much highertemperatures, thereby providing cooling and fire extinguishingproperties. The composites have mechanical and structural integrity andmay be used in conjunction with penetration resistant materials or, insome cases, can be designed to provide some penetration resistance.

SUMMARY OF THE INVENTION

The preferred composites described herein comprise a substrate materialcomprised of woven, layered or intertwined polarized strands of glass,polyamide, polyphenylene sulfide, carbon or graphite fibers on which ametal compound comprising a coordinated complex compound of a polar gasrefrigerant and sorbent comprising a metal salt or a metal hydroxide ispolar bonded on the surface of the fibers and/or strands atconcentrations sufficient to form bridges of the metal compound betweenadjacent substrate strands and/or substrate fibers. Single or multiplelayers of the metal compound bonded fibers are coated with a coatingmaterial capable of preventing release or escape or increase inconcentration (e.g. water) of the internal gaseous refrigerant atexternal atmospheric or ambient pressure but which is capable ofallowing penetration of the refrigerant at internal refrigerantpressures resulting in total internal pressure of at least about 15% ormore above exterior atmospheric/ambient pressure. Panels comprisinglaminates or other shaped geometries may be produced using compositelayers. When heat is imposed on the composite via fire, explosion,directed energy, combustion of gasoline, oil, other liquid or gaseous orsolid fuels, rocket fuel or by a projectile breaching the exteriorcoating, causing a temperature increase of the bonded metal compound anda resulting increase in internal composite pressure, the compositereleases refrigerant. Such refrigerant release will cool the compositeand may prevent ignition of protected contents and/or personnel orextinguish a flame. Panels comprising multiple layers having differentsorbents and/or different refrigerants with different refrigerantrelease temperature/pressure ranges may be produced to achieve thermalgradient refrigerant release at selected temperatures.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The unique refrigerant releasing composite products described herein arepreferably fabricated from a substrate material comprising preferablywoven or intertwined polarized strands or layered strands of thesubstrate. Such woven or intertwined substrate material incorporate orutilize elongated or continuous fibers such as fabrics or cloth orunwoven intertwined fiber materials such as yarn, rope or the like wherethe fibers or strands of fibers have been twisted or formed in acoherent form such as yarn or weaves of strands. Various or differentweaving patterns may be used, preferably three-dimensional weaves whichyield multi-directional strength characteristics as compared totwo-dimensional weaves having anisotropic strength characteristics. Thepreferred substrate utilizes elongated and/or continuous fibers orfilaments as opposed to chopped or loose fibers or strands in whichthere is no interlocking or structural pattern to the fibrous substratein order to achieve good mechanical strength. However, non-woven fibersincluding mat, batting, felt or chopped or loose fiber materials areuseful for the purpose of refrigerant release composites, but offer lessmechanical strength or penetration protection. Suitable materials alsoinclude needle woven layers of substrate fiber strands. Alternatively,layers of elongated, substantially continuous fiber strands which havenot been woven in a three-dimensional weave may be used. Successivelayers of the fibers are preferably positioned along different axes soas to give the substrate strength in multiple directions. Moreover, suchlayers of non-woven fibers can be positioned between layers of wovenfibers.

The substrate material of which the fiber strands are made includeglass, polyamide, polyphenylene sulfide, carbon or graphite fibers.Glass fibers are a preferred fiber material, woven glass fibers beingrelatively inexpensive and woven glass fiber fabric easy to handle andprocess in preparing the composites. The glass fibers may be E-glassand/or S-glass, the latter having a higher tensile strength. Glass fiberfabrics are also available in many different weaving patterns which alsomakes the glass fiber material a good candidate for the composites.Carbon and/or graphite fiber strands may also be used. Polyamidematerials or nylon polymer fiber strands are also useful, having goodmechanical properties. Aromatic polyamide resins (aramid resin fiberstrands, commercially available as Kevlar® and Nomex®) are also useful.Yet another useful fiber strand material is made of polyphenylenesulfide, commercially available as Ryton®. Combinations of two or moreof the aforesaid materials may be used in making up the substrate, withspecific layered material selected to take advantage of the uniqueproperties of each of them. The substrate material, preferably has anopen volume of at least about 30%, and more preferably 50% or more, upto about 95%. The specific substrate material selected and used as wellas the percentage of open volume may depend on the expected uses,including environmental exposure conditions, substrate meltingtemperatures, and the like.

The surface of the fibers and fiber strands of the aforesaid substratematerial must be sufficiently polarized to at least provide some bondingbetween the fiber and the absorbent crystals adequate to achieve thebelow loading densities. Polarized fibers are commonly present oncommercially available fabrics, weaves or other aforesaid forms of thesubstrate. If not, the substrate may be treated to polarize the fiberand strand surfaces. The surface polarization requirements of the fiber,whether provided on the substrate by a manufacturer, or whether thefibers are treated for polarization, must be sufficient to achieve aloading density of the metal salt or hydroxide on the fiber of at leastabout 0.3 grams per cc of open substrate volume whereby the bonded metalcompound bridges at least some adjacent fiber and/or adjacent strands ofthe substrate. Polarity of the substrate material may be readilydetermined by immersing or otherwise treating the substrate with asolution of the salt or hydroxide, drying the material and determiningthe weight of the metal compound polar bonded to the substrate.Alternatively, polar bonding may be determined by optically examining asample of the dried substrate material and observing the extent of metalcompound bridging of adjacent fiber and/or strand surfaces. Even priorto such bonding determination, the substrate may be examined to see ifexcessive oil or lubricant is present on the surface. Oil coatedmaterial will substantially negatively affect the ability of thesubstrate fiber surfaces to form an ionic, polar bond with a metal saltor metal hydroxide. If excessive surface oil is present, the substratemay be readily treated, for example, by heating the material tosufficient temperatures to burn off or evaporate most or substantiallyall of the undesirable lubricant. Oil or lubricant may also be removedby treating the substrate with a solvent, and thereafter suitably dryingthe material to remove the solvent and dissolved lubricant. Substratesmay also be treated with polarizing liquids such as water, alcohol,inorganic acids, e.g., sulfuric acid.

The substrate may be electrostatically charged by exposing the materialto an electrical discharge or “corona” to improve surface polarity. Suchtreatment causes oxygen molecules within the discharge area to bond tothe ends of molecules in the substrate material resulting in achemically activated polar bonding surface. Again, the substratematerial should be mostly free of oil prior to the electrostatictreatment.

A sorbent for the polar gas refrigerant comprising metal salt, or metalhydroxide, is bonded to the surface of the polarized substrate materialby impregnating, soaking, spraying, flowing, immersing or otherwiseeffectively exposing the substrate surface to the metal compound. Apreferred method of bonding the sorbent to the substrate is byimpregnating, soaking, or spraying the material with a liquid solution,slurry or suspension or mixture containing the metal salt or hydroxidefollowed by removing the solvent or carrier by drying, heating and/or byapplying a vacuum. The substrate may also be impregnated by pumping asalt or hydroxide suspension, slurry or solution or liquid-salt mixtureinto and through the material. Where the liquid carrier is a solvent forthe salt, it may be preferred to use a saturated salt solution forimpregnating the substrate. However, for some cases, lowerconcentrations of salt or hydroxide may be used, for example, wherenecessitated or dictated to meet permissible loading densities. Wheresolubility of the salt or hydroxide in the liquid carrier is notpractical or possible, substantially homogeneous dispersions may beused. Where an electrostatically charged substrate is used, the salt orhydroxide may be bonded by blowing or dusting the material with dry saltor hydroxide particles.

As previously described, it is necessary to bond a sufficient amount ofmetal salt or metal hydroxide on the substrate to achieve at least somebridging of the salt or hydroxide crystal structure between adjacentfibers and/or strands. A sufficient amount of salt or hydroxide isprovided by at least about 0.3 grams per cc of open substrate volume,preferably at least about 0.4 grams per cc, and most preferably at leastabout 0.5 grams per cc of open substrate volume, which is between about30% and about 95% of the untreated substrate volume, and preferablybetween about 50% and about 95%. Following the aforesaid treatment, thematerial is dried in equipment and under conditions to form a flatlayer, or other desired size and shape using a mold or form. A driedsubstrate will readily hold its shape. Unless the solvent is also therefrigerant, drying to substantially eliminate the solvent, carrierfluid or other liquid is necessary, although small amounts of fluid, forexample, up to 1-2% of solvent, can usually be tolerated withoutdetriment to the strength or refrigerant holding capacity of thematerial. Drying and handling techniques for such solvent removal willbe understood by those skilled in the art. If the solvent is also therefrigerant, the solvent removal may be stopped at the desired level ofrefrigerant content. The most preferred refrigerants are water andammonia.

Typical mass percentages of refrigerant mass per dry sorbent mass arebetween about 5% and about 80%. Hydroxides commonly do not absorbammonia and are limited to water refrigerant of just one or a few molesof water per mole of hydroxide. Exposure of these compounds to heatcauses a rise in refrigerant pressure and can be employed to release therefrigerant in the typically endothermic process. Heats of reactionrange form about 35 kJ/mol ammonia for relatively high vapor pressureammoniated complex compounds to over 70 kJ/mol water for hydratedcomplex compounds and select ammoniated compounds and even higher forhydroxide hydrates and even higher for the reduction of hydroxides intooxides, such heats of reaction absorbing often over 100 kJ/mol of water.

Metal salts or hydroxides bonded to the substrate are alkali metal,alkaline earth metal, transition metal, zinc, cadmium, tin, aluminum,double metal salts of the aforesaid metals, and/or mixtures of two ormore of the metal salts. The salts of the aforesaid metals are halide,nitrite, nitrate, oxalate, perchlorate, sulfate or sulfite. Thepreferred salts are halides, and preferred metals are strontium,magnesium, manganese, iron, cobalt, calcium, barium and lithium. Theaforesaid preferred metal salts provide molecular weight/electrovalent(ionic) bond ratios of between about 40 and about 250.

Unless the solvent is identical to the refrigerant and was intentionallyretained during the drying process, to form a coordinated complexcompound of a bonded metal salt or hydroxide and a polar gaseousrefrigerant, the substrate material having the bonded metal salt orhydroxide (sorbent) formed as previously described is treated with theselected gaseous refrigerant which becomes absorbed on the sorbent. Suchabsorption reactions and the coordinated complex compounds are describedin substantial detail in U.S. Pat. Nos. 5,298,231, 5,441,716 and6,224,842, the descriptions of which are incorporated herein byreference. The preferred polar gas to be absorbed onto the metal salt toform the compound is selected from ammonia and water. Other ligands,such as amines and alcohols are also possible, but usually lessdesirable due to their flammability and low heat of reaction resultingin a lesser cooling effect. Phosphine is another polar gaseousrefrigerant that may be used in special circumstances because of itstoxicity. The specific polar gas refrigerant to be absorbed on thespecific sorbent will depend on the temperature range desired to triggeror initiate release of the polar gas to achieve the desired coolingeffect on the composite at the time it is exposed to heat by fire,explosion, directed energy, fuel combustion or is hit by a bullet,shrapnel or other invasive material causing a temperature rise. Forexample, to extinguish a flame, water may be the preferred refrigerantto be released by the composite. When metal hydroxides are used water isthe only practical refrigerant forming the related hydrates and with theadditional release at the highest temperature converting the hydroxideinto the corresponding oxide. However, complex compounds with water asthe polar refrigerant and hydrated metal hydroxides commonly releasewater at higher temperatures compared to the temperatures at which morevolatile refrigerants such as ammonia or amines are released. Where itis desired for relatively low temperature refrigerant release, forexample, between about 150° F.-400° F., ammonia refrigerant is useful,whereby the ammoniated complex compounds as previously described may beused. Because different ammoniated complex compounds will release(desorb) ammonia at different temperatures, the specific metal salt(sorbent) as well as the coordination step of the ammoniated complexcompound may be selected depending on the desired refrigerant releasetemperature. For higher temperature refrigerant release, for example, inthe temperature range between about 200° F.-800° F., water may be therefrigerant absorbed on the metal salts to form the complex compounds.Complex compounds of different metal salts and water will release waterat different temperatures as will complex compounds of one metal salthaving different water coordination spheres or steps. Thus, the specificabsorbents and/or refrigerants and/or complex compound coordinationsteps may be selected depending on the specific refrigerant releasetemperature range desired. For yet higher temperatures, the release ofwater from a hydrated metal hydroxide may be used, e.g., sodium, calciumor lithium hydroxide hydrates. For example, hydrated metal hydroxidesmay release water at temperatures above 300° F. up to 1,000° F. At evenhigher temperatures, metal hydroxides may release water by converting tothe corresponding oxide at temperatures up to about 2,000° F. Somehydroxides, however, will melt at or below 2000° F. thus likelyreleasing water.

As described, since refrigerants are released at different temperatureranges depending on their ligand sphere or chemical bond , it may bedesirable to form a composite having different layers or laminates oflayers of metal compounds using the same or different refrigerantshaving selected different absorbents yielding different ligandcoordinating complex compounds, or other metal compounds such ashydroxides. For example, different ammoniated complex compounds and/ordifferent hydrated complex compounds and/or hydroxides and/or hydratedhydroxides may be used in different layers of a composite. Moreover, thecomposite may be configured so that successively higher (or lower)temperature refrigerant release complex compounds and/or hydroxides areused in successive layers of the composite structure. It may also bedesirable to utilize different refrigerants in different successivelayers of the compounds so as to achieve a selected successive releaseof refrigerants at progressively higher temperatures. Such compositescomprise multiple layers with two or more different layers and two ormore different metal compounds. Such different metal compounds areselected from different complex compounds comprising different metalsalts with one refrigerant, different metal salts with differentrefrigerants, one metal salt with different refrigerants or one metalsalt with different coordination spheres of one refrigerant; hydratedmetal hydroxides; and metal hydroxides. A composite having combinationsof the aforesaid metal compounds, e.g., between two and six differentmetal compounds, may be used to release refrigerants at any number ofdifferent successive temperatures. Thus, such composites having selectedthermal profile or thermal refrigerant gradient may release refrigerantgas or gases at controllable conditions to provide cooling andextinguish flame at such selected different specific triggertemperature/pressure conditions. Preferred composites for suchprogressive temperature refrigerant release will incorporate anammoniated complex compound and/or a hydrated complex compound, and/or ahydrated metal hydroxide, and/or a metal hydroxide. The benefits of suchan effect, whether using different refrigerants, different sorbents orboth at such different and progressive temperatures, or using a singlerefrigerant composite, will be evident. For example, containers,cylinders, boxes or cases made from such a composite may be used forprotecting many kinds of ordnance or other valuable and/or fragilematerial such as ammunition, fuel and missiles as well as personnel.

Where the metal compound is an ammoniated complex compound of theaforesaid salts, and which are listed in U.S. Pat. No. 5,441,716, thedegree of coordination is important in that it determines the coolingenergy density potential as well as the mechanical ruggedness andintegrity of the composite. Higher degrees of ammoniation tend to reducethe mechanical ruggedness and strength and the composites capability toserve as armor or protective matter. Where a greater amount ofrefrigerant is desired, a higher coordinated step product may be used,and for a reduced quantity of refrigerant, a lower coordination step maybe suitable. The same holds true for complex compounds in which therefrigerant is other than ammonia. Similarly, where the refrigerant iswater, and a hydrate is used, the amount of hydration may be selected toachieve the desired amount of water vapor available when the refrigerantis released. However, hydrates are more susceptible to losing mechanicalintegrity and strength with increased hydration level. The compromisebetween cooling energy density and mechanical strength and protectivecharacteristics of the composite needs to be more carefully evaluatedfor each application than for ammoniated compounds.

If not previously sized, the material is cut to form layers of a desiredsize and/or shape, and each layer of metal compound bonded substratematerial or multiple layers thereof are sealed by coating with acomposition capable of preventing the penetration of gaseous refrigerantfrom the composite through the coating at ambient/atmospherictemperature and pressure and preventing water absorption by exposure toambient atmospheric conditions, but which is capable of refrigerantpenetration and release at a temperature increase that causes internalrefrigerant partial pressure increase resulting in total internalpressure above exterior atmospheric or ambient pressure sufficient forthe refrigerant to penetrate the coating. Typically, such total internalpressure will result in total pressures exceeding atmospheric pressureby about 15% or more. The coating step should be carried out underconditions or within a time so as to substantially seal the compositethereby preventing the complex compound or hydrated metal compound fromdeterioration by being exposed to atmospheric conditions which couldcause liquefaction and/or loss of the salt bond and structural integrityof the product. As previously stated, the coating composition must becapable of preventing premature release of gaseous refrigerant from thecomposite at ambient temperatures and ambient atmospheric pressure.However, the coating composition must also allow for release andpenetration of the refrigerant when the internal pressure of thecomposite is increased above the atmospheric/ambient pressure such ascaused by the composite exposed to heat from fire, explosives, fuelcombustion or caused by impact from shrapnel, bullets, projectiles, orother such events causing internal compound temperature and relatedpressure increase and resulting in the complex compound or metalhydroxide releasing the bonded refrigerant from the composite structure.The breached coating may vaporize, melt, fracture or otherwise becomeporous to the gaseous refrigerant released by the metal compoundpreviously protected by the coating composition. Such coating must beconfigured to allow for such release or penetration of the gaseousrefrigerant where the total internal pressure exceeds exteriorambient/atmospheric pressure (ΔP) by 15% or more up to even 500% or1,000% or more. Typically, such ΔP will result at internal compositetemperature of about 150° F. and preferably above about 200° F. or moreor, in case of higher temperature ammoniated complex compounds or selecthydrated compounds or hydroxides, such temperatures can exceed 500° F.,1,000° F. or even reach 2,000° F. Suitable coating compositions includeepoxy resin, phenolic resin, neoprene, vinyl polymers such as PBC, PBCvinyl acetate or vinyl butyral copolymers, fluoroplastics such aspolychlorotrifluoroethylene, polytetrafluoroethylene, FEPfluoroplastics, polyvinylidene fluoride, chlorinated rubber, and metalfilms including steel alloys, aluminum and zinc coatings. The aforesaidlist is by way of example, and is not intended to be exhaustive. Again,the coating may be applied to individual layers of substrate, and/or toa plurality of layers or to the outer, exposed surfaces of a pluralityor stack of substrate layers. When different sorbents and/or differentrefrigerants are used each such composition is preferably sealed bysealant to avoid undesired migration of refrigerant from one sorbent tothe other or mixing or displacement of one refrigerant with the other,

Panels or other forms and geometries such as concave, convex or roundshapes of the aforesaid coated substrate composites such as laminatesare formed to the desired thickness. Moreover, such panels or laminatesmay also provide ballistic protection and may be installed in doors,sides, bottoms or tops of a vehicle, around ammunition, sensitive cargo,etc. to provide such protection as well as the above described coolingand fire extinguishing properties. Panels may also be shaped for otheruses including personnel protection items and may be assembled in theform of cases, cylinders, boxes or containers for protection ofordnance, explosives, rockets, missiles, directed energy, such as laserbeams or other materiel, fragile or sensitive items. Laminates mayinclude layers of steel or other ballistic resistant material such ascarbon fiber composites, boron carbide, aramid composites or metalalloys.

The aforesaid composites may be readily molded into articles havingcontoured and cylindrical shapes, specific examples of which includehelmets, helmet panels or components, vests, vest panels as well asvehicle protection panels, vehicle body components, rocket or missilehousings and rocket or missile containment units, including NLOS (nonline of sight) systems. Such housings and containment units would encaseand protect a rocket or missile and are used to store and/or firemissiles or rockets and could be constructed using the compositesdescribed herein to protect their contents from external objects such asbullets or bomb fragments. Vest panels of various sizes and shapes maybe formed for being inserted into pockets located on or in the lining ofexisting or traditional military vests. The combined use of such panelswith more traditional bulletproof vests may result in a lighter, moreflexible, and more readily adaptable vest that accommodates the varietyof sizes for different individuals. Similarly, one embodiment is ahelmet panel that has been contoured to fit inside as a liner for atraditional helmet. In another embodiment, the protective compositepanel is secured on the outside of the helmet with flexible and/orresilient helmet covers, netting, etc. In a different embodiment, thehelmet may include one or more contoured or shaped composites asdescribed herein to protect the wearer from bullets or bomb fragments.Again, water is the preferred refrigerant for such composites.

Panels of the aforesaid may be used for shielding soft shelters forpersonnel such as tents of various sizes and capacities includingcommand posts as well as shelters for munitions, telecommunicationequipment, etc. Release of refrigerant, such as water, from such panelsmay provide time for personnel to escape from a shelter exposed to heatfrom explosion or fire.

For penetration resistant vehicular armor, many different sized andshaped protection panels may be formed of the composite including floor,door, side and top panels as well as vehicle body components contouredin the shape of fenders, gas tank, engine and wheel protectors, hoods,and the like. As used herein, “vehicle” includes a variety of machines,including automobiles, tanks, trucks, helicopters, aircraft and thelike. Thus, the penetration resistant vehicle armor may be used toprotect the occupants or vital portions of any type of vehicle.

The aforesaid composite articles may also be combined with otherballistic and penetration resistant panels of various shapes and sizes.For example, the aforesaid composites may be paired with one or morelayers or panels of materials such as steel, aramid resins, carbon fibercomposites, boron carbide, or other such penetration resistant materialsknown to those skilled in the art including the use of two or more ofthe aforesaid materials, depending on the armor requirements of thepenetration resistant articles required.

For composites mostly intended for non-ballistic and maximum thermalprotection, additional refrigerant may be provided by incorporatingspheres, compartments, packets or small reservoirs of pure liquidrefrigerant or liquid refrigerant solutions in one or more layers,chambers or cavities with the most preferred refrigerant being water.The liquid containing layer or layers may be configured to release theliquid refrigerant or solution at the lowest temperature end thecomposite is designed and configured to provide protection for. Therelease of such refrigerants, e.g., water, ammonia, alcohols, amines, orrefrigerant solution, e.g., alcohol-water, ammonia-water, aqueousbrines, will occur when such a composite is exposed to elevatedtemperature causing internal refrigerant release and penetration,typically above 150° F. Such a modified composite must be designed toseal such liquid from the substrate/metal compound layers to prevent anysuch liquid from contacting, penetrating or permeating into thesubstrate under normal, typical ambient conditions. It is also importantthat the coating of adjacent layers prevents the released refrigerantfrom penetrating the coating and being reabsorbed onto the sorbentunderneath the coating which would not only offset the cooling achievedvia the evaporation of the refrigerant but adversely effect the systemby generating the heat of absorption in the absorbing material therebyactually generating net heat due to exothermic reaction. If thecomposite incorporating such additional liquid refrigerant orrefrigerant solution is to be used or exposed to conditions requiringballistic protection, exterior panels, layers or other armor protectionwill be required to prevent exterior ballistic penetration of thecomposite.

1. A composite panel configured to release refrigerant therefrom,comprising: a substrate material comprising one or more layers ofpolarized fibers; a metal compound bonded to said substrate materialcomprising a complex compound of a polar gaseous refrigerant and a metalsalt, and/or a hydrated metal hydroxide and/or a metal hydroxide; and acoating composition sealing at least one layer of said substratematerial, and/or the exterior surface of said composite, and configuredto prevent release of internal gaseous refrigerant therethrough atambient temperatures and pressure and allow penetration and release ofgaseous refrigerant at increased pressure within the composite panel. 2.A composite panel of claim 1, wherein the increased pressure is aninternal gas pressure of 15% or more above exterior pressure.
 3. Acomposite panel of claim 1, wherein said compound is at a concentrationof at least about 0.3 grams/cc of open substrate material volume.
 4. Acomposite panel of claim 1 comprising a panel of body armor configuredto protect a person.
 5. A composite panel of claim 1 comprising astructural panel configured to protect personnel and/or ordnance and/orheat sensitive items.
 6. A composite panel of claim 4 wherein the polargaseous refrigerant comprises water.
 7. A composite panel of claim 5wherein the polar gaseous refrigerant comprises water.
 8. A compositepanel of claim 1 wherein said composite further incorporates one or morelayers containing liquid water or water solutions sealed from contact orpermeation thereof into the substrate with the coating composition underambient temperature conditions.
 9. A composite panel of claim 7 whereinsaid composite further incorporates one or more layers containing liquidwater or water solutions sealed from contact or permeation thereof intothe substrate with the coating composition under ambient temperatureconditions.
 10. A composite panel of claim 1 wherein the panel comprisesa vehicle protection panel.
 11. A composite panel of claim 1 wherein thepanel comprises a vehicle body component.
 12. A composite panel of claim1 wherein the fibers comprise glass, polyamide, polyphenylene sulfide,carbon or graphite or combinations of two or more thereof
 13. Acomposite panel of claim 1 wherein the metal compound comprises alkalimetal, alkaline earth metal, transition metal, zinc, cadmium, tin,aluminum or combinations of two or more thereof
 14. A composite panel ofclaim 1 wherein the polar gaseous refrigerant comprises ammonia,alcohol, amine, or water.
 15. A composite panel of claim 1 wherein saidfibers are woven, layered or intertwined strands of fibers orcombinations of two or more thereof
 16. A composite panel of claim 1wherein the polarized fibers comprise aromatic polyamide resin fibers.17. A composite panel of claim 1 comprising a panel or shaped articleconfigured to protect ordnance.
 18. A composite panel of claim 1comprising a soft shelter and wherein said polar gas refrigerantcomprises water.
 19. A composite panel of claim 18 wherein saidcomposite further incorporates one or more layers containing liquidwater or water solutions sealed from contact or permeation thereof intothe substrate with the coating composition under ambient temperatureconditions.
 20. A composite panel of claim 1 configured to releaserefrigerant therefrom at progressively elevated temperatures comprisinga first portion of said substrate material having a first complexcompound bonded thereon capable of releasing refrigerant in a firsttemperature range, and a second portion of said substrate materialhaving a second complex compound bonded thereon capable of releasingrefrigerant in a second temperature range, higher than said firsttemperature range.
 21. A composite panel of claim 20 further comprisinga third portion of said substrate material having a hydrated metalhydroxide or a metal hydroxide bonded thereon capable of releasingrefrigerant in a third temperature range, higher than said first andsecond temperature ranges.
 22. A composite panel of claim 1 configuredto release refrigerant therefrom at successively elevated temperaturescomprising a first portion of said substrate material having a complexcompound bonded thereon capable of releasing refrigerant in a firsttemperature range, and a second portion of said substrate materialhaving a hydrated metal hydroxide or a metal hydroxide bonded thereoncapable of releasing refrigerant in a second temperature range, higherthan said first temperature range.